Certain para-menthylcyclohexanol ethers of certain glycols



NOV. 13, 1951 M E GROQTE ET 2,574,539

CERTAIN PARA-MENTHYLCYCLOHEXANOL ETHERS OF CERTAIN GLYCOLS Filed Nov. 1, 1949 lOO o WWW MENTHYLCYCLOHEXANOL C l- O IOO% uooz,

IN VEN TORS MELVIN DEGROOTE ARTHUR F WIRTEL A TTORNEY Patented Nov. 13, 1951 CERTAIN PARA-MENTHYLCYCLOHEXANOL ETHERS OF CERTAIN GLYCOLS Melvin De Groote, University City, and Arthur F. Wirtel and Owen H. Pettingill, Kirkwood, Mo, assignors to Petrolite Corporation, Ltd., Wilmington, DeL, a corporation of Delaware Application November 1, 1949, Serial N 0. 124,812

The present invention is concerned withcertain new chemical products, compounds, or composition which have useful application in various arts. It includes methods or procedures for man-' ufacturing said new chemical products, compounds or compositions, as well as the products, compounds or compositions themselves.

We have discovered that if one treats para-- menthylcyclohexanol with a combination of propylene oxide and ethylene oxide within the proportions hereinafter specified, the mixedmenthylcyclohexanol glycol ether so obtained is an-unusually effective demulsifying agent for water-in-oil emulsions, and also has utility in various other arts hereinafter described. 1 One specific example exemplifying the herein contemplated compounds is the product obtained by reacting one pound mole of para-menthylcyclohexanol with 23 pound moles of propylene oxide, followed by reaction with 27 pound moles of ethylene oxide. Such oxyalkylations are usually conducted in the presence of an alkaline catalyst. This specific compound just mentioned is one of a series of similar compounds having, in the main, the same general structure or composition.

Previous reference has been made to the fact that the herein specified products are of particular value forresolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring Waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

This specific application or use of our reagents is described and claimed in our co-pending application Serial No. 124,811, now Patent No. 2,558,510, filed November 1, 1949.

-The compounds herein described are not only useful for breaking oilfield emulsions, but also are useful for various other purposes, such as a break-inducer in the, doctor treatment of sour hydrocarbons, as an emulsifying agent, as a component in the preparation of micellar solutions, asan additive to non-hydrocarbon lubricants, as an intermediate for further reaction by virtue of the terminal hydroxyl radical, etc.

It is well known that a variety of compounds containing a reactive hydrogen atom, i. e., a hydrogen atom attached to oxygen, nitrogen, or sulphur will react with alkylene oxides, particularly ethylene oxide or propylene oxide, to yield the corresponding glycol or polyglycol derivative. Such oxyalkylated derivatives are readily prepared from chemical compounds in which the hydrogen atom is directly attached to oxygen, and particularly in the case of alcohols or phenols', such as aliphatic alcohols, phenols, alkylaryl alcohols, alicyclic alcohols, phenoxyalkanols,

a cam.) (01. 260-611) substituted phenoxyalkanols, etc. Generally speaking, it has been found advantageous to react a water-insoluble hydroxylated material, having 8 carbon atoms or more, with an alkylene r oxide so as to introduce water-solubility, or at least, significant or distinct hydrophile character, with the result that the derivative so obtained has surface-active properties.

Examples of suitable reactants of this typeinclude octyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, octadecyl alcohol, butylphenol, propylphenol, propylcresol, hexylphenol, octylphenol, nonylphenol, and cardanol, as well as the corresponding alicyclic alcohols obtained by the hydrogenation of the aforementioned phenols. It has been suggested that at least some of such materials be used in the resolution of petroleum emulsions. As far as we are aware,

none of such materials represent products which are acceptable in demulsification today from ,a

competitive standpoint. In the majority of cases.

such products are aptto be one-sixth, one-fifth,

one-fourth, or one-third as good as available de mulsifying agents on the same percentage-of active-material basis, or same cost basis.

We have discovered a very few exceptions tio the above general situation. For example, .we

have discovered, if one treats para-menthylcycloa certain range, as hereinafter specified. 'A specific exemplification of this range is the product obtained by treating one mole of paramenth'yl cyclohexanol with 23 moles of propylene oxide,

' and then with 27 moles of ethylene oxide. Slim ilarly, one may treat the para-menthylcyclov" hexanol with'the 27 moles of ethylene oxide first and then with the 23 moles of propylene oxide next.

1 In subsequentparagraphs from time to time reference is made to compounds or cogeneric mixtures. Atfirst glance it may appear that such language is indefinite, and, perhaps, con

tradictory. It is the intention at the moment only to point out that there is no inconsistency in such description, and that subsequently, there will be a complete explanation of why such designation is entirely proper. A

The cogeneric mixtures of glycol ethers of paramenthylcyclohexanol are unusually eifective de--v mulsifying agents on a comparatively small num-, ber of oil field emulsions, which, oddlylenough,- appear rather widely distributed geographically.

These para-menthylcyclohexanolether mixtures do not appear to be universally competitive, and,

as a matter of fact, appearto be highly selective; in regard vto their action asdemulsifying agents.

However, such products have significant utility in a number ofdifiZerent oil "fields .where they serve better .than'iany other available'ldemulsiiy: ing agent. Their utility may, of course, increase as time goes along.

Para-menthylcyclohexanol is obtained ,by the hydrogenation of menthylphenol.""Theprocedure is essentially the same as employedin theccin ,yclphexanol with 23.5 moles of propylene oxide,

followed by treatment with 27.5 moles of ethylfene 'oxide.

version of phenol to cyclohexanol. :Menthylphenol has been supplied by-the l-lerculeslPowder Company, Wilmington, Delaware. The formula of menthylphenol is believed to be "asfollows'z' 1?" 131.1? product dbtaiuedby vhydn n tiq o "'In'spite of-the unique character of the cominoundspreviously described, we have made additionally aninvention within an invention. This "can be illustratedby reference to the compounds "'orcogene'ric mixtures whose composition is determinedhy the inner triangle 2, 4, 5. This preferred class of derivatives, or, for that matter, all

3 the -herein described products, can be made in amuse. t e o respond ng yclo exano to w t.

menthylcyclohexanol, ,the formula of .whiQh as fell ws;

The molecular weight of para-menthylcyclohexanol is 232; the commercial product actually shows a molecular weight'slightly more. For convenience, we have taken-the molecular Weight of-th'c'commercial-product as 238.

It is very peculiar that the effectiveness of the demulsifying agents herein described seemto be limited to avery narrow range or area, as far as composition goes; Reference is "made to the ac companying drawing, in which there is presented a triangular graph showing the composition of certain glycol 'menthylcyclohexanol, or 'cogenericsmixtures'thereof, derivable from para-menthylcyclohexanol and ethylene oxide alone, or para-menthylcyclohexanol and propylene oxide a'ldxie, or para-menthylcyclohexanol and ethylene oxide' intermsof the initial reactants. We have found that efiective dmulsifying agents lie approximately within a small and hitherto unsuspected area indicated by the trapezoid determiried'by the points 8', 8;- HI' and I fl, More specifically,"particularly effective demulsifying agents appear within a smaller range, as set forth -ap-' proximately by the area indicated by the segment of 'acircle in which the area ofthe-segment is limited to derivatives in which menthylcyclohexanol contributes at least 4% by weight of the ultimate compound. "The circle itself is identified by the fact that the points' l, 3 was appear on thecircle. The more effective of these b'etter compounds' or co generic mixtures are those wh'ichappear within the triangle which representspart of tl'ie circle and part of the segment, to wit, the triangle identified by the points 1 3 and GI' I'he most erfective compounds or cogeneric mixtures of allare those which fall within the inner central tri angle of :the larger outer triangle identified by. the points I, 3 and .6,'to wit, the smaller triangle identified by the points :2, 4 and 5. The most outstanding of these effective compounds .or. no-

gerieric mixtures is one which appears. to fell three different ways: (,a) by adding propylene oxide first andthenethyleheoxide; K12) b addil the ethylene oxide firstalld then, propylene oxide;

0111c) by adding .the =,two oxides by random, different. or uncontrolled addition so as to pro,- ducea.noly lyeoliether. in whi h h pm y ene radicals or ethylene radicals dov not appear in eontinuoussuccession but are h t r ee eously distributed.

WBJDBMGiQ -I IC th t propylene xid s added first and then ethylene oxide is added, that the 7 omp undssoobtained a e nvariably an merit:

ably more refte tiveas d mu s fie s, d a a so more effective for other pu p ses than. any ot er comparable lycol ethers of parazm n l yclehexanol made Joy combinin he th ee reactants This will be e p ained, further -=with additiona llustrations subseque As illustration ,of :the pr parati o yarieust mpounds. or Qp eneric mixtures, an p ni larlyihemostdesirablepnes.and also those w h.

in, any other se encearelhelpfiullnzsetting the i h r mme.- viouslv r ferred to, thei'ollow ns xamples are.

included. .In cozmectionrwith these examial s itwill be dotedyllhalmthe oxyalkylation. often- 4 menthylcycloh xanol. .ie... by tr men with ethylene. oxide rorlpmnylene xid ,or. a m xt re the two, is conventionalv The proced r i an:

ducted in the samesrnapner emplo vin ned:

tion with "other alcohols .or the like, and gener ally. an alkaline catalyst is employe See, for

example, 11. R tent Na--2ili4l1fl9ldated Ap il 20, .1943. tolsrael, and British Patent No. 6 91 7 applied fonFebruaz ssl-znl li V V Example 1 rer' operated ata speed of approximately .250

R. R. M. There were charged into the autoclave 23.8 pounds of para-menthylcyclohexanol. There were then added one pound 3 ounces (approxh mate1y- 5 by weight) ofground caustic soda.

The autoclave was sealed, swept with nitrogen gas, and stirring started immediately. and heat 7 applied, and the temperature allowed to rise to approximately C. Atithis point the addition of "propyleneoxide was started. It was added cone tinuously. at such speed that it was absorbed by the reaction as rapidly as added. The amount of'propylene oxide added was 136 pounds. Thetime required to add this propylene oxide was slightly in excess of'one hour, about 1%, hours. During (this time thetemperature was maintained at 1,503 to using cooling water through the inner coils when necessary and otherwise applying. heat, if required. At the end of the addition, of. the propylene oxide. there; was. added ethylene 2 V The, capacity was approximately 4.0 gallons. Thestiroxide, previously indicated;v The amount of ethylene oxide added was 120.5 pounds. Thetemperature employed, and operating conditions, were the same as with the addition of propylene oxide. It is to be noted, however, that ethylene oxide appears to be more reactive and the reaction seems to require a greater amount of cooling water to hold the temperature range as indicated. The time required to add the ethylene oxide was about the same, or slightly less, usually just a little more than an hour. 7

During the addition of the oxides the pressure was held at approximately 50 pounds per square inch gauge pressure, or less. When all the oxide had been added (ethylene oxide being the final addition in this particular instance) the autoclave was permitted to stay at the-same temperature range, for another half hour, even longer, if required, or until the gauge pressure had been reduced to zero, or substantially zero, indicating the reaction was complete.

The final product was an oily material, somewhat viscous in nature, and having a sort of greenish hue, without any definite odor. It was dispersible in water and soluble in non-aqueous solvents, such as aromatic hydrocarbons and others, although not soluble in some non-polar hydrocarbon solvents. The final yield was substantially the total weight of the initial reactants.

Example 2 The same procedure was followed as in Example 1, preceding, except that the order of addition of the oxides was reversed, the ethylene oxide being added first and the propylene oxide last. The time period, temperature range, pressure, etc., were kept the same as in Example 1, preceding.

Example 3 Examples! The same procedure as in Example 1, preceding was conducted on a laboratory scale, employing 6 a small autoclave having a capacity of approximately one liter, up to a 5-gallon size. The

amount of paramenthylcyclohexanol employed.

was 47.6 grams, the amount of propylene oxide employed was 2'72 grams, and the amount of ethylene oxide employed was, 241 grams. The amount of caustic soda employed was 2.4 grams. The operating conditions were substantially the same as on a larger scale. Actually, the reaction seemed to go faster in the small autoclave and the time of absorption could be reduced, if desired.

In many instances, absorption would take place in the laboratory autoclave in a fraction of the time required in the larger autoclave; in fact, in many instances, absorption was completein 5 to 10 or minutes, as compared to one hour on a larger scale. Needless to say, on a large scale, addition must be conducted carefully because there is an obvious hazard in handling a large quantity.

of material in an autoclave which is not necessarily present in the use of a small vessel.

Easample 5 The same procedure was followed as in Example 4, preceding, in every respect, exceptthevariation described in Example 2, preceding, 1. e., the ethylene oxide, was added first and the propylene oxide added last.

Example 6 The same procedure was followed as in Example 4, in every instance except the modification previously described in Example 3, to wit, the propylene oxide and the ethylene oxidefwere mixed together and-added in approximately '15 minutes to one-half hour. In all other respects Menthylcyclohexanol Propylene Oxide Ethylene Oxide Point a e Wt. Pei Wt. Per Wt. Per Ex.-N0. y s

Wt. Used Molal ggs, Wt. Used Molal t fr Wt. Used Molal ifif specific in Grams Ratio Glycol in Grams Ratio Glycol in Grams Ratio Glycol Glycol Ether Ether Ether Ethers A 238 l. 0 15.0 715 12.32 635 14. 43 40 1 B. 238 1.0 10.0 1, 192 20.55 953 21. 40 2 C. 238 1. 0 5.0 2, 620 45.15 55 1, 910 43. 3 40 3 D. 238 1. 0 10.0 1, 071 18. 50 45 1, 071 24. 38 45 4 E 238 1. 0 5.0 2, 382 41. l 50 2, 140 48. 6 45 6 F 238 1. 0 5. 0 2,145 37.0 45 2, 380 54. 2 50 1,6 CL.-. 238 1. 0 8. 5 1, 360 23. 42 48.5 1, 205 27. 4 43 7 H- 238 1. 0 9. 2 1, 258 21. 64 48. 6 092 24. 82 42. 2 (l) I. 238 1. 0 9.0 255 21.62 47. 4 1, 154 26. 2 43. 6 1.. 238 1. 0 4.8 248 21.5 46. 2 1, 218 27.65 45.0 g1) K" 238 1. 0 8. 6 356 23. 38 49.0 1, 202 27.3 43, 4 G.- 238 1. 0 8. 5 360 23. 42 48. 5 l, 205 27. 4 43. 0 Z 7 L 238 1. 0 8.4 321 22. 46. 6 l, 275 29. 0 45. 0 (1; M. 238 1. 0 8 2 438 24. 75 49. 5 l, 230 27. 42. 3 (1 N 238 1.0 8.0 444 24.86 48. 5 l, 295 29.4 43. 5 O. 238 l. 0 7. 8 446 24.90 47. 4 l, 370 31.15 44. 8 (1) P. 238 1. 0 7.0 668 28. 72 49.0 1,496 33.05 44.0 (1) Q- 238 1. O 8. 0 1, 965 33. 90 49. 5 1, 766 40. 2 44. 5 (1) R 238 1.0 20. 0 309 5. 33 26. O 643 14. 6 54. 0 3 8 S... 238 1. 0 4. 0 1 548 26.7 26.0 4, 94. 7 70.0 3 9 1.- 238 1.0 4.0 4 520 77. 8 76.0 1, 27.0 20.0 3 10 U 238 1. 0 20. 0 714 12. 3 60. 0 238 5. 42 20. 0 5 11 1 Within inner triangular area. i Duplicated ior convenience. 3 Indicates limits oi trapezoidal area.

the preparation of the above compounds the alkaline-catalyst used was either flakecaustic soda finely ground with mortar and pestle, or powdered sodium methylaite, equivalent to by weight of the para menthy'lcyclohexanol which was employed.

For reasons which are-pointed out hereinafter in'grea'ter detail, it is substantially impossible to use conventional methods and obtain a single glyod'l 'ether of the kind'described. Actually, one obtains-a cogeneric mixture of closely related or touching horno'logues. -'These materials invariably have high :mol'ecular weights andcannot be separated from :one another by an-yknown method without decomposition. {The properties of such a iriixture represent the contribution of theivarious individual members of the mixture.

tfilthough :one cannot draw a single formula andisay tha't by following such and such procedura one c'an obtain80'% or 90% 'or:l00% ofsllch single compound, yet one can readily 'drawthe.

l en and to "If one selects any hydroxylated compound and subjects such compound to oxyalkylation, such as oxyethylation or oxypropylation, it-becomes obvious thatone is really producing a polymer of the alkylene oxide, except for the terminal group. This. isparticularly true where the amount of oxide added is comparatively largeyfor instance, 10,20, 30,40, or B-Ounits. If such a compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that from instances where n has a value .of :25 and perhaps less, to a point where'n may represent35 1 or more. Such mixture is, as stated, a cogeneric,

closely related series "of touching homologous. Considerable investigation has been compounds. made in regard to the distribution curves for' linear polymers. Attention is directed to the anticle entitled Fundamental Principles of Gender!- sation Polymerization, .by Paul J. Flory, which appeared in Chemical Reviews, volume 39, No.1, page 137.

Unfortunately, as has been pointed out by V. Flory and other investigators, there is no satisfactory method, based on either experimental or mathematicalexamination, of indicating the exact proportionofthe various members oftouching homologous series which appearin cogeneric condensation products of the kind described. This means that from the practical standpoint, i. e., the ability to describe'how to make the pro duct under consideration and how to repeat such :cogeneric mixture must result.

production time after time without difficulty, it is necessary to resort to some other method 'of description.

Actually, from a practical standpoint, it'is much more satisfactory, perhaps, to describe the ultimate'composition interms of the reactants, -i.;e., menthylclohexanol and the two alkylene oxides] The reason for this statement isthe following! If one selects a specific compound, it must be bornein mind that such compound isspecific only insofar that the cogeneric mixture,,i n terms of a statistical average, will conform to this formula. Thisvmay be illustratedby anexample' such as ROfLCsHeOlzflCzl-MO)21H. If one com-.-

bines thereactants in the predetermined .Weight,

ratio so as to give theoretically this specific component, and assuming only one'chemical compound wereformed, what happens is that,',al-

though this particular compound may be present in asignificant amount and probably less than 50%, actually, one obtains a cogeneric mixture of touching homologues, in which the'statistical averagedoes correspond to this formula. For

instance, selecting reactants, which, at least theoretically, could give the single compound RO(C3H6'O) 23(C2H40) 21H, what actually happens is, that one obtains a sort of double cogeneric mixture, .ior .the' reason that in each batchwor continuous addition of alkylene .oxide, a mem eri c mixture is formed. Since the present pro ducts require the addition of at least two difierent multi-molar,proportionsof each of two different alkylene oxides, (ethylene oxide and propylene oxide)',*it' becomes obvious that a rather complex Thiscan be best illustrated by example. As-

sume'that one'is going to use the indicated ratio,

to wit, one pound mole of menthylcyclohexanol,

.23 pounds of propylene oxide and '27 pounds of ethylene oxide. treatment of-one pound moleof menthylcyclo- The initia1--step involves the ihexanol With 23 pound moles of propylene oxide .150 as to yield theoretically..RO(C3H6O)z3H; V

actually, as pointed out, one does not obtaini .:RO(C3HsO)-1iH in which n is.23, .but one obtains "1a cogeneric mixture, in which'there are present one does not obtain a single constituent, which, 1

for the sake of convenience, maybe indicated as RO.(C2H4O 30H. Instead, one obtains a cogeneric mixture of -.closely .relatedhomologues, in which the formula may be shown as the following: RO(C2H4O)nH, wherein as far as the statistical average goes, is'30, but the individual members present in significant amount may vary 'significant amounts of homologues in-which n .varies from l0, l1 and 12, on up to 35, 36 and possibly 40, or beyond. Astatisticalaverage, however, must, of course, correspondto. the proportion of the initial reactants i. e., 'a'compound of the formula RO(C3H60)23H, which is present undoubtedly to a significant extent.

When this cogeneric mixture is then subjected 9 to reaction with 27 moles of ethylene oxide, it becomes obvious that, although One may obtain some RO(C3H6O)23(C2H4O)27H, yet this particular product can only be present to a minor extent for reasons which have been described in connection with oxyethylation and which now are magnified to a greater degree by oxypropylation. Stated another way, it is probable that the cogeneric mixture represents something like RO(CaHsO)n(C2H4O)1uI-I in which, as previously pointed out, components present in important percentages are those in which n could vary anywhere from 10 or higher, up to 35 or 40. By the same token, components present in important percentages are those in which n could vary any- I where from 13 or 14, and possibly even less, up

to 40, 41, 42, 43 or 45. Indeed homologues of a lower or a higher value of n and n will be present in minor amounts, the percentages of such components decreasing, the further removed they are from the average composition. However, in spite of such variation in regard to the cogeneric mixture, the ultimate composition, based on the ingredients which enter into it and based on the statistical average of such constituents, can still be expressed by the formula RO(CsHaO) z: (C2H4O) 27H This actual product exists, to some degree, in the cogeneric mixture, but it should be looked upon as a statistical average formula, rather than the structure of a single or predominant compound in the mixture.

A second reason for employing a reaction mixture to describe the product, is the fact that the molal proportions need not represent whole numbers. selects molal proportions corresponding to then the constituents are added in actual molar course, would be immaterial, for the reason that if one starts with a pound mole of menthylcyclohe'xanol and adds 23.5 pound moles of propylene oxide, one will obtain, on the average, a mixture closely comparable to the one previously described, using exactly 23 pound moles of propylene oxide instead of 23.5. Such mixture cor- :responds to the compound RO(C3H60)23.5H only in the sense of the average statistical value, but not in the sense that there actually can be a compound corresponding to such formula. Further discussion of thisfactor appears unnecces- 'sfi' 'y, in light of what has been said previously.

Such mixture could, of course, be treated with 2'7 pound moles of ethylene oxide. Actually, all that has been said sums up to this, and that is, that the most satisfactory way, as has been said before, of indicating actual materials obtained by the usual and conventional oxyalkylation process,

is in terms of the initial reactants, and it is obvious that any particular point on the triangular graph, from a practical aspect, invariably and inevitably represents the statistical average of several or possibly a dozen or more closely related -c"ogeners of ahnost the same composition, but

representing a series of touching homologues.

The particular point selected represents at least the composition of the mixture expressed empirically in the terms of a compound representing the statistical average.

Previous reference has been made to the fact that comparatively few oxyalkylated derivatives of simple hydroxylated compounds find utility in actual demulsiflcation practice. We have pointed out that we have found a very few exceptions to this rule. The fact that exceptions exist, as in the instant invention, is still exceedingly difficult to explain, if one examines the slight contribution that the end group, derived from the hydroxylated material, makes to the entire compound. Referring, for the moment, to a product of the kind which has been described and identified by the formula RO(C3H60)23(C2H40)27H, it becomes apparent that the molecular weight is in the neighborhood of 2900, and actually, the paramenthylcyclohexanol contributes less than 10% of the molecular weight. As a matter of fact, in other comparable compounds the para-menthylcyclohexanol may contribute as little as 4% or 5%, and yet these particular compounds are effective demulsifiers. Under such circumstances, it would seem reasonable-to expect that some other, or almost any other, substituted cyclic fi-carbon atom compound comparableto We have just pointed out that if one para-menthylcyclohexanol, would yield derivatives equally effective. Actually. this is .not the case. We know of no theory or explanation to suggest this highly specific nature or action of the compound or cogeneric' mixture derived from para-menthylcyclohexanol.

Referring to an examination of the previous list of 32 compounds, it is to be noted that in certain examples, for instance, Examples 9 to 15, inclusive, all the propylene oxide is added first and then the ethylene oxide is added. Compounds indicated by Examples 1 to 8 are substantially the same, as far as composition goes, but are reversed, insofar that the ethylene oxide is added first and then the propylene oxide. Other compounds having substantially the same ultimate composition, or at least, very closely related .ultimate compositions, having a further variation to 32, inclusive. 4

As has been pointed out previously, for some reason which we do not understand, and for which we have not been able to offer any satisfactory theory, we have found that the best compounds, or, more properly, cogeneric mixtures, are obtained when all the propylene oxide is added first and then all the ethylene oxide is added. Although this is true to at least some extent, in regard to all compositions within the trapezoidal area in the triangular graph, yet it is particularly true if the composition comes within the segment of the circle previously referred to in the drawing. In such event, one obtains a much more effective demulsifier than by any other combination employing ethylene oxide alone, propylene oxide alone, or any variation in the mixture of the two, as illustrated by other formulae. In fact, the compound, or cogeneric mixture so obtained, as far as demulsification is concerned, is not infrequently at least one-third better thanany other derivative obtained in the manner described involving any of the other above variations.

The significance of what has been said previously becomes more emphatic when onerealizes tam-4, 589

thatjinessence, we have found that one isomer -:is a :more effective demulsif-ying agent than "another fisomerf The word isomer is not-ex.- actly right, although it is descriptive for the purpose intended, insofar that we arenot concerned with 'a single compound, but with a -cogeneric ,:-mixture, which, in its statistical average, corresponds to such compound. Stated another way,

if we'start with one I-poundmole of methylcyclo- :hexanol, 23 pound moles of propylene oxide and -27 pound moles of ethylene oxide, we can pre- ,pare two different cogeneric mixtures, which, on

'astatisticalaverage, correspond to the following:

RIO (C2H40') 23 (CaHsO )27K and V RO(C3H6Q) 23,(C2H4O) 21H There. .is nothing we know which would :suggest that the latter be-a much more effective demulsifying agent; than the former, and also that-it be 124,814,.both filed November 1., 1949..

which the mixed statistical average would. correspond' closely to, point. 1.,

We need not. add that insteadv of subjecting menthylcyclohexanol alone to ox'yethyla'tion, and oxyprop'ylati'on, or inversely, oxyprop ylation and 'oxyethylation, "or a simultaneous 'treatmen'tof both oxides, one can employ a mixture of menthylcyclohexanol along with some other desired reactant, such as alpha-terpirieol. For 'a number of reasons, it is, ordinarily desirable to use a procedure in which only one product is reacted at a time. I

Previous reference has: been made to the fact that. the herein. described products or compounds have utility in fields other than demulsification. Since these products contain a terminal hydroxyl, they can, of course, be used as 'a source of new derivatives by reaction with acids, other oxides, such. as phenyl ethylene oxide (styrene oxide), and the like. Such acids may' be monocarboxy or polycarboxyr, such as phthalic anhydride. The products maybe used as assistants in forming emulsions, particularly emulsions which approach micellersolutions. Anexample of such emulsion is the following:

Emulsion. Example A1 Grams -Product of Example;1....e-- ae 8.9

Sodium elea I I I. a 16.0

Sodium carbonates is... "hone 1.6

Water a 22.0

. :Kerosene a 51,5

' abledemulsifying, agents for resolution of. water-c :In the preparation of the-above emulsion the "sodium carbonate is dissolved in the water and: then the sodium .oleate dissolved completely.

After this -mixture has been prepared, the prodnot of Example -1 is then added and mixed'until the mass is entirely homogeneous. kerosene is added slowly, withconstant stir-ring,

. until a completely smooth emulsion is produced.

We-also desire to point out that veryefieotive demulsif-ying agents andrdemulsifying agentsfcan be-obtained from. compounds of the kind ;de scribed by enhancing their water-solubility by the introduction of a sulfo group. For instance, two ,moles of any of the described derivatives can be reacted with one. mole of .maleicanhydride so as to give.thecompleteester. Thiscom- .plete ester can then be treated in the conven-.

tional mannerwith sodium bisulfite so v.as to give the corresponding. manner with. sodium. 'hisulfite so asto give the corresponding sodiumsulfo-suceinate in the form. of asodiumsalt. What has been said regard to thesefcofnpounds as demulsifiers also applies in regardto V compound is within the area designated by the segment of the circle in the drawing. I

Throughout the specification elsewhere, reference has been made to homologues. It is quite likely that it would be equally proper in numerous instances, and perhaps all the herein :described products, to refer to isomers as well as homologues. The reason for this'statement is that propylene oxide, as differentiated from ethylene oxide, can, at least-theoretically, combine with a hydroxylated material ROH to give two different derivatives, one being a primary alcohol and the other a secondary alcohol. This isillustrat'ed by the following:

11 H "Hum,-

OER H H H l non n O-CCH; Ho-C-0cm Elsewhere in the. specification the word isomer has been used thus: isomer. 'not believed there is any confusion between such terminology in that particular instance and what-issaid immediately preceding.

Attention is directed to the fact that the herein described compounds, compositions and the like which are particularly adapted for use as demuls'ifi'ers' for water-in-oil emulsions, as found in the petroleum industry, are hydroxylated derivatives, i. e., carry or includes. terminal hydroxyl radical, as part of their structure. vWe. have found that if. such hydroxylated compound or compounds are reacted. further so as to produce entirely new derivatives, such new derivatives have the properties of the original:hydroxylated compound, insofar that. they are effective and valuin-oil. emulsions, as found in the. petroleum industry, as break inducers doctor treatment 01? sour crude, etc. 7 y I Such hydroxylated compounds can be treated with. various reactants such-as glycide, epichlorohydrin, dimethyl sulfate, sulfuric acid, 'maleic anhydrideethylene imine, etc. 'If treated. with Then the to yielda su fo-succinate. introduced also by means of a sulfating agent, as previously suggested, or by treating the chloroacetic acid resultant with sodium sulfite. "--However, the class of derivatives most readily prepared in wide variety are the esters of mono- 'carboxy and polycarboxy acids.

from hydroxyacetylated the resultant can be treated with sodium bisulfite Sulfo groups can be Assumins, a typical derivative which can be indicated thus:

the ester of the monocarboxy acid is as follows:

The acid ester of a dicarboxy acid is as follows:

-Thecomplete ester of a dicarboxy acid is as follows:

The chloroacetic acid ester is as follows:

The quaternary compound obtained by reacting the above-mentioned product with pyridine is as follows:

Among the various kinds of monocarboxy acids Typical acids exemplifying this tional equivalent, such as the acylchloride, the

anhydride, the ester, the amide, etc., may be z'employed.

4 Another class of esters are those obtained from -certain drastically-oxidized hydroxyacetylated castor oil fatty acids.

The drastically-oxidized acetylated ricinoleic acid compounds are employed to furnish the acyl radical of the ester. In

this particular instance, as in all other instances-- one may prepare either a total ester or a partial ester, and when carboxy acids are employed one may have not only partial esters which have re-.-

sidual hydroxyl radicals or residual carboxyl A somewhat similar type of ester is obtained drastically-oxidized castor oil fatty acids. It is to be pointed out that hydroxy-ac'etylation may take place first, and drastic oxidation subsequently, or the reverse may be true, or both procedures may be conducted simultaneously. In any event, such prodherein included.

"Another somewhat similar class are esters obtained from hydroxyacetylated drasticallyoxidized dehydrated ricinoleic acid. In this class ricinoleic acid, castor oil, or the like is subjected to dehydration as an initial step. Such products may be employed to supply the acyl radical of one type of ester herein included.

Another type of ester which may be employed is a sulfo-fatty acid ester, in which there is present at least 8 and not more than 22 carbon atoms in the fatty acid radical. The sulfo-radical includes both the acid sulfonates and the sulfonic acids. Briefly stated, suitable sulfo-acids herein employed as reactants are sulfo-oleic, sulforicinoleic, sulfo-aromatic fatty acids obtainedjor example, from benzene, toluene, xylene, etc., and oleic acid or some other unsaturated acid.

Another class of acids are polycarboxy acids, suchas commonly used in forming plasticizers, polyester resins, etc. One may use a tricarboxy acid, such as tricarballylic acid, or citric'acid, but our preference is to employ a dicarboxy acid, or acid anhydride, such as oxalic acid, maleic acid, tartaric acid, citraconic acid, phthalic acid, adipic acid, succinic acid, azeleic acid, sebacic acid, adduct acids obtained by reaction between -maleic anhydride, citraconic anhydride, and butadiene, diglycollic acid, or cyclopentadiene. Oxalic acid is not quite as satisfactory as some of the other acids, due to its tendency to decompose. In light of raw material costs, it is our preference to use phthalic anhydride, maleic anhydride, citraconic anhydride, diglycollic acid, adipic acid and certain other acids in the same price range which are both cheap and heatresistant. One may also use adduct acids of the diene or Clocker type.

Another class of esters are derived from certain high molal monocarboxy acids. It is well known that certain monocarboxy organic acids containing 8 carbon atoms or more, and not more than 32 carbon atoms, are characterized by the fact that they combine with alkalies to produce soap or soap-like materials. These detergent-forming acids include fatty acids, resin acids, petroleum acids, etc. For the sake of Convenience, these acids will 'be indicated by the formula R.COOH. Certain derivatives 'of detergent-forming acids react with alkali to produce soap or soap-like materials and are the obvious equivalent of the unchanged orunmodified detergent forming acids. For instance, instead of fatty acids, one might employ the chlorinated 5 fatty acids. Instead of the resin acids, one might employ the hydrogenated resin acids. Instead of naphthenic acids, one might employ brominated naphthenic acids, etc. i

' The fatty acids are of the type commonly referred to as higher fatty acids; and, of course, this is also true in regard to derivatives of the kind-indicated, insofar that such derivatives are obtained from higher fatty acids. The petroleum acids include not only naturally-occurring naphthenicacids, but also acids obtained by the biddatiori of wax, parafiin', etc. Such acids may have as many as 32 carbon atoms. For instance, see'U. S. Patent No. 2,242,837, dated May 20, 1941, to Shields.

The monocarboxy detergent-forming esters of the oxy-alkylated derivatives herein described, are preferably derived from unsaturated fatty acids having 18 carbon atoms. Such unsatu- "rated. fatty acids include oleic acid, ricinoleic acid, linoleic acid, etc. One may employ mixed fatty acids, as, for example, the fatty acids obthe .acyl radical.

tained from hydrolysis of cottonseed @oll, -so yabean oil, :etc. Itisour ultimate preference that the esters of the kind herein contemplated be derived from unsaturatedfatty acids, and more especially, unsaturated fatty acids containing'a hydroxyl radical, or unsaturated fatty acids which have been subjected to oxidation. .In addition to synthetic carboxy acids obtained by the oxidation of paraflins or the like, .there is the somewhat analogous class obtained by treating carbon dioxide or carbon monoxide, in the presence of hydrogen or an olefine, with steam, or-by causing a halogenated hydrocarbon to react with potassium cyanide and saponifying the product obtained. Such products or mixtures thereof, having at least 8 and not more than 32 carbon atoms, and having at least one carboxyl group or the equivalent thereof, are suitable as detergent-forming monocarboxy acids; and another analogous class equally suitable is themixture of carboxylic acids obtained by the alkali treatment of alcohols of high molecular weight formed in the catalytic hydrogenation of carbon -monoxide.

One may have esters derived not only from a single class of acids of the kind described, but

also from more than one class, i. e., one may employ mixed esters such as esters obtained, for example, from high molal detergent-forming .acids having 8 to 22 carbon atoms, as previously described, in combination with acids of the alpha- .halogen carboxy type having less than 8 carbon :atoms, such as chloroacetic acid, bromoacetic,

vac-id, etc., as previously described.

. Drastically-oxidized oil, such as drasticallyoxidized castor oil, or drastically-oxidized dehydrated castor oil, may be employed to supply In other instances, one may produce mixed esters by using polycarboxy acids,

such as phthalic acid, diglycollic acid, etc., in

combination with detergent-forming acids, such -as oleic acid, stearic acid, naphthenic acid, etc.

Other carboxy acids may be employed in which there is also a sulfo group present, such as sulfo- :phthalic sulfo-benzoic,sulfo-succinic,-etc. Esters may be obtained from low molal hydroxylated acids having less than 8 carbon atoms, Such as hydroxyacetic acid, lactic acid, etc. Similarly, one may employ low molal aliphatic acids having less than 8 carbon atoms, such as acetic acid, =butyric acid, etc. Similarly, one may employ low molal acids having the vinyl radical, such as .acrylic acid, methacrylic acid, crotonic acid, etc.

It 'will be noted that these acids contain various numbers of acyl radicals varying generally up to 22 carbon atoms ,for the monocarboxy acids, and as many as 36 carbon atoms in the case of certain polycarboxy acids, particularly the dimer obtained by the dimerization of 9,11-octadecadienic acid. As to this particular product, see

. pr 2% ef para-toluene sulfonicracid along with a phase-separating trap .until the amountoi Y indicates the reactionis completepor substantially complete. The time required is usually --4 to 20 hours. Such esters are, as previously stated, very efiective for'resolution of water-in oil emnlsions, as found in the petroleum industry.

The triangular graph represents the threecomponent system. Usingxi reactants,.i.-.e.,-:.the three depicted in the triangular :graph, "P1115 glycide, gives a four-reactant system which j'y-ields derivatives for demulsification of water-.in-oil emulsions at least equal to'those herein described.

The use of glycide'in a four-componentreactent. permits unusual structure, as, for :example, a

variety of furcation. Thus, the .hydroxylated initial reactant can be .treated with glycide in the conventional manner, using an alkaline catalyst, and after an introduction 'of a tmole-fitob mole ratio of' glycide, then propylene oxide can be introduced in the mannerpreviously described,

and thereafter ethylene oxide can be added. If desired, the propylene oxide can be introduced first and then one mole of glycide added, followed by ethylene oxide, or both procedures can be employed. 7

Moreover, glycide can be used to replace a'sub-' stantial part or greater part of the ethylene oxide, or propylene oxide, or both. suchcom pounds can .be converted into various derivatives of the kind previouslydescribed. Under such circumstances, reaction with glycide and an end reactant to supply a terminal radical is not considered as forming a derivative but'a's simply forming the end material. The ester and similar derivatives so obtained from the four-component original system, i. e., the ones including glycide,

are also very effective for demulsificatio'n pf water-in-oil emulsions, as found inthe 'ciI'fm dustry.

Having thus described our invention, what we claim as new and desire to secure by Letters Pat ent is:

l. A cogeneric mixture of'a homologous seriesof glycol ethers of para-menthylcyclohexanol;

said cogeneric mixture being derived exclusively from para-menthylcyclohexanol, ethylene .oxide and propylene oxide in such weight proportions so the average composition 'of said cogeneric-mixture stated in terms of initial reactants lies .ap-

proximately Within the trapezoidal area {defined 3 .approximately inxthe accompanying drawing by points8, 9,10 and I I.

2. A cogeneric mixture of a homologous of glycol ethers of para-menthylcyclohexanol;

said cogeneric mixture being derived exclusively from para-menthylcyclohexanol, ethylene pxide and-propylene oxide in such weight proportions so the average composition of said cogenericmixture stated in terms of initial reactants lies -a.p-

proximately within the segment .of the circle in the accompanying drawing in which the :minimum para-.menthylcyclohexanol content :is net least 4% and whichcircle is;identifie d by-the.iaet;

that points-1,3 and x6 lie-on its circumference.

3. A cogenericymixtureof a homologous series of glycol ethers of para-menthylcyclohexanol;

said cogeneric mixture being derived exclusively. 7 from paraementhylcyclohexanol, ethylene oxide and propylene oxide in such weight proportions so the average composition of-said-cogenericzmtxture stated in terms .of Tinitial reactants .li'esiapproximatelywithin the triangular area defineddn the accompanying drawing by points I, 3 audit.

4. A cogeneri'c mixture of a homologous series of glycol ethers of para-menthylcyclohexaml;

said cogeneric mixture being derived exclusively from para-menthylcyclohexanol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the triangular area defined in the accompanying drawing by points 2, 4 and 5.

5. A cogeneric mixture of a homologous series of glycol ethers of para-menthylcyclohexanol; said cogeneric mixture being derived exclusively from para-menthylcyclohexanol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately at point 1 in the accompanying drawmg.

6. A single cogeneric mixture of a homologous series of glycol ethers of para-menthylcyclohexanol; said cogeneric mixture being derived exclusively from para-menthylcyclohexanol, ethylene oxide and propylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately at point 1 in the accompanying drawing.

- MELVIN DE GROOTE.

ARTHUR F. WIRTEL. OWEN H. PETTINGILL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,976,677 Wittwer Oct. 9, 1934 2,176,834 Bruson Oct. 17, 1939 2,213,477 Steindorf et al Sept. 3, 1940 2,425,755 Roberts et a1 Aug. 19, 1947 2,425,845 Toussaint et a1 Aug. 19, 1947 

1. A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF PARA-MENTHYLCYCLOHEXANOL; SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM PARA-MENTHYLCYCLOHEXANOL, ETHYLENE OXIDE AND PROPYLENE OXIDE IN SUCH WEIGHT PROPORTIONS SO THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE STATED IN TERMS OF INITIAL REACTANTS LIES APPROXIMATELY WITHIN THE TRAPEZOIDAL AREA DEFINED APPROXIMATELY IN THE ACCOMPANYING DRAWING BY POINTS 8, 9, 10 AND
 11. 